CN1040188A - The fire-resistant product that refractory aggregate improves to some extent with low temperature bonding immunomodulator compounds and normal temperature strength - Google Patents

The fire-resistant product that refractory aggregate improves to some extent with low temperature bonding immunomodulator compounds and normal temperature strength Download PDF

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Publication number
CN1040188A
CN1040188A CN89104047A CN89104047A CN1040188A CN 1040188 A CN1040188 A CN 1040188A CN 89104047 A CN89104047 A CN 89104047A CN 89104047 A CN89104047 A CN 89104047A CN 1040188 A CN1040188 A CN 1040188A
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refractory aggregate
binder
weight
refractory
aryl
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詹姆斯·温莎·斯坦德拉
基思·布里杰
托马斯·爱德华·罗洛森
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Martin Marietta Magnesia Specialties LLC
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Martin Marietta Magnesia Specialties LLC
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • C04B35/657—Processes involving a melting step for manufacturing refractories
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • C04B35/6306—Binders based on phosphoric acids or phosphates

Abstract

The present invention relates to refractory phosphorated organic adhesive immunomodulator compounds, the method for preparing this binder compound, the standby refractory materials-binder material of pre-mixing with long storage life limit uses the method for this pre-mixing refractory materials and the high-strength fireproof base substrate of producing with this premixed refractory materials.

Description

The fire-resistant product that refractory aggregate improves to some extent with low temperature bonding immunomodulator compounds and normal temperature strength
The present invention relates to refractory with phosphorous organic adhesive immunomodulator compounds, the method of the binder compound that preparation is suitable for, fire-resistant-matrix material premixed, standby, that have the long storage life limit, the method for using said pre-mixing refractory materials and the high-strength fireproof goods of producing by said pre-mixing refractory materials.
As everyone knows, refractory materials has two big classes: non-basic refractory (for example pure aluminium silicate) and basic refractory (for example periclasite, magnefer and magnesite), they all are mainly to be made up of CaO and/or MgO.
Various materials are as low temperature (for example 400-2000) Chemical Felter in the alkaline refractory products, so that be provided at the following binding material of low temperature that can not directly bond and be shaped by sintering.The better example of these materials is water glass, chromic acid and various inorganic phosphorous compound.These compounds must be dissolved in the liquid medium just works effectively.In the practicality, said liquid medium must be a water, because these binder materials generally are insoluble to non-aqueous media (in organic solvent).In addition, most non-aqueous medias also have some other shortcomings, for example flammable, toxicity and costing an arm and a leg.These binder materials only are applicable to preparation on the spot and the basic refractory that uses immediately so far.Water is as liquid medium, but only with the alkaline bone material short-time contact because immediately mixture heating up is anhydrated so that remove after the loading of kiln.The example of these products is blasting materials, ramming material and mould material, is solid under these material dried forms.Because these products mix the use of existing side by side promptly on the spot with water, so these products do not need to demonstrate the shelf-life of remarkable length under blended or wet condition.
Past never successfully produced and wherein contained premixed, the standby alkaline fire-resistant ramming/repairing mixture that is evenly distributed with Chemical Felter by liquid phase.This is because alkaline refractory aggregate contacts instability for a long time with water.MgO and CaO all react with water, generate Mg(OH respectively) 2And Ca(OH) 2These reactions make the refractory mixture of pre-wetted have following all problems:
1. hydration causes volumetric expansion (destruction structure of refractory), is decomposed into particle;
2. hydration reduces free water content, and binding material begins to condense too early;
3. hydrate high temp decomposes down explosion hazard.
Basic refractory can not the fresh water supply system pre-mixing, and can not look to these materials to demonstrate the shelf-life.The variety of problems that makes fresh water supply system blended basic refractory must prepare on the spot and follow to avoid hydration immediately.When such in-field use, only use water as the medium of refractory materials loading of kiln, mixture heating up is removed anhydrated immediately.
United States Patent (USP) the 4th, 473 discloses for No. 654 and to have used lithium compound and siccative oil and so on organic materials production to have the pre-mixing basic refractory of long storage life limit.But this patent does not rely on the phosphorus between the refractory aggregate bonding, and this matrix material needs 5% free CaO at least so that effectively work.
People know that also use resol and pitch and so on organic materials bonds between alkaline refractory aggregate.But because this cohesive action depends on the carbon of burning under the oxidizing condition, its refractory product intensity is reduced, also be restricted so resol and bituminous use.
Use inorganic P contained compound known in the art, for example the aqueous solution of sodium phosphate or potassiumphosphate as the fire-resistant Chemical Felter of alkalescence.Binding agent although it is so and alkaline refractory aggregate form very strong chemical bonding effect, but in fact these compounds are only soluble in water and shortcoming discussed above is arranged.Work and to be dissolved in them in the water.Therefore, alkalescence is fire-resistant-and the inorganic phosphate salt mixture all must prepare on the spot and use immediately, so there is not the shelf-life basically.
Use acid phosphite binder material when disclosing the use refractory among the Japanese Patent 49-10967 simultaneously.These adhesive materials form suitable ceramic bonding effect between non-alkaline refractory.But, because these matrix materials contain acidic hydrogen, produce chemical reaction when using these matrix materials with alkaline refractory, therefore this fire bond mixture is gone up the no shelf-life substantially.Moreover disclosed phosphite has high-vapor-pressure in this piece patent, so this material breakdown generates the potential evaporation before of phosphorus binding agent.Though this Patent publish uses phosphite, it is believed that these salt are generally only water-soluble, thereby stop these materials to continue to be exposed among the basic refractory that this causes because of hydration problem discussed above.
In view of the foregoing and for overcoming in the prior art all shortcomings made the present invention.
One object of the present invention be to provide the neutral organophosphate of non-water basically and phosphoric acid ester, its salt with and its homopolymer and multipolymer as the binding agent (including but not limited to alkaline refractory aggregate) of refractory aggregate.
Another purpose of the present invention is to provide preparation to be suitable for the method for the binder compound of the object of the invention.
Another object of the present invention is to provide the standby refractory materials of the pre-mixing/binder compound material with long storage life limit.
Still a further object of the present invention is the method that used high temperature furnace lining in the purposes such as using premixed refractory materials building, reconstruction and repairing steel-making will be provided.
The last purpose of the present invention is to provide the high-strength fireproof of being made by premixed refractory materials base substrate.
In order to obtain to satisfy the binding agent phase that is suitable for of following standard, studied several binder systems shared with ceramic refractory:
1) this tackiness agent must be basically with the refractory aggregate reaction, especially at room temperature over a long time in alkaline refractory aggregate reaction (generally be in the common storage period of refractory aggregate mixture 1 thoughtful 2 years scope in);
2) this binding agent must or can the dissolved solid phase exist in organic solvent with liquid phase;
When 3) heating, this tackiness agent must decompose before boiling, formed the material that contains reactive phosphorus.
Preferred binding agent except that above-mentioned all standards also should be, its degradation production does not have to be smelt and nonirritant concerning installation comprises the workman of fire-resistant product of said binding agent.
The various organic chemicals that form phosphoric acid ester or phosphonic acid ester binding material have been tested; But some is easy to and alkaline refractory reaction in these organophosphorus compoundses and the phosphonic acid ester, therefore is unsuitable for providing the binding agent/aggregate mixture with long storage life.
Said inapplicable compound, feature are the hydrogen atoms with acid, shown in the general formula of following phosphoric acid ester that provides respectively and phosphonic acid ester:
Exist the hydrogen atom of acid to make these compounds not be subjected to the influence (R is an organic group) of R kind easily with alkaline refractory aggregate reaction.Therefore, phosphoric acid ester or phosphonic acid ester binding agent should not contain the hydrogen atom of acid.
Found a class neutral organophosphate and phosphonic acid ester, its salt and the polymkeric substance thereof of non-water basically after the further investigation of processes such as the inventor, this class material at room temperature is difficult for reacting with basic refractory but forms stable binding agent mutually.Therefore, this tackiness agent can be used for preparing stable alkaline refractory aggregate/binder mixtures, and this mixture can be pre-mixed with long storage and preserve.
This class binder material comprises neutral organophosphate and phosphonic acid ester, its salt and polymkeric substance thereof, at room temperature they do not react with basic refractory, can obtain with liquid phase or organic solvent dissolution solid phase form, and before volatilization, decompose during heating, form the compound that contains the non-volatility phosphoric acid ester.
First " group " compound is a neutral phosphate in these binder compounds, and its general formula is as follows:
R in the formula 1, R 2And R 3Between can identical or different (following note R 1=, ≠ R 2=, ≠ R 3).Said organic group R 1, R 2And R 3Comprise the alkyl of alkyl, aryl, replacement and the aryl of replacement, select the alkyl and the aryl of these alkyl, aryl and replacement, make phosphoric acid ester satisfy above-mentioned standard 2 by certain way) and 3).Go up or interior substituting group comprises one or more functional groups (but being not limited thereto) at alkyl (or aryl):
In addition, R 1Also can be connected to R 2Or R 3On provide following illustrative the sort of cyclic group:
Figure 891040471_IMG11
R 1, R 2Or R 3Also can be connected other phosphate-based on, form as following illustrative polyphosphoric acid ester group:
Figure 891040471_IMG12
Perhaps form the ring-type poly phosphate, for example
Figure 891040471_IMG13
Note, in the compound that a plurality of P groups are arranged, R x(x=1,2,3 or 4) group and R n x(n=', " or) group can be grouped into by identical or different one-tenth.In a word, R n xThe R that group comprises and lists above xThe composition that group is identical.
In addition, R 1, R 2Or R 3Can be polymer-based group, for example:
Figure 891040471_IMG14
Wherein x is the polymerization degree, and its value is 1～1000.The further combination of above-mentioned group is also feasible.In addition, also can use wherein phosphate-based direct interconnected polymeric phosphoric acid ester, for example:
Figure 891040471_IMG15
R wherein 1=, ≠ R 2=, ≠ R 3=, ≠ R 4
Second " group " these binder compounds are neutral phosphonic acid esters, and its formula is as follows:
Figure 891040471_IMG16
R wherein 1=, ≠ R 2=, ≠ R 3R 1, R 2And R 3Identical during with top discussion phosphoric acid ester group of selection and scope.
The 3rd " group " binder compound that the present invention includes is to have the phosphonate that shows general formula down:
M wherein 1=, ≠ M 2The phosphonate that the present invention includes is M wherein 1And M 2For comprising the metal ion of sodium (Na), potassium (K) and lithium (Li).As long as the compound that generates exists with liquid form or exists with the solid form that can be dissolved in the organic liquid, other metal ion also can use.Introduce R in the selection of R and scope and the top phosphoric acid ester " group " 1, R 2And R 3Time regulation identical.Note R, R 1, R 2Or R 3Not only can comprise phosphate-based but also can comprise phosphonate group, so also can be mixed ester.
Preferred substituted is an oxygen-containing substituents, and this substituent adhesive compound is general to produce harmless degradation production (as CO because comprise 2, H 2O etc.), and do not produce by containing the issuable pungency degradation production of the substituting group of element outside the aerobic (as HCl etc.).In addition, oxygen-containing substituents can make binding agent reach the standard of listing above easily.The binder compound of summarizing above many of the present invention does not generally have disagreeable smell and pungency, but its degradation production may not be like this.During hot repair, in the time of will repairing mixture and be added in the hot stove, there is mechanism to be calcined fully and discharge by factory's cigarette gathering system.Therefore, the possibility that is exposed in the degradation production of people is minimum.But in some cases, when serving as a contrast furnace lining again, inner lining of furnace may be awfully hot, and causing binder decomposed, so the installation personnel in the stove will be exposed among the steam of emitting.For this purposes, binding agent and its degradation production be nonirritant but also do not have objectionable odor not only.When using the chloro phosphoric acid ester, HCl is main degradation production, and its steam is irritating.We find, (for example the phosphoric acid ester of the replacement of ethers-O-or alcohols-OH) can satisfy the technological standard 1-3 that lists above only to contain oxygen in the functional group except carbon and hydrogen.These esters resolve into CO 2And H 2O and do not have or almost do not have smell and pungency.
A kind of preferred matrix material example comprises any material of listing standard 1-3 above satisfying.Preferred binder material example comprises neutral chloro phosphoric acid ester, neutral chloro phosphoric acid ester, neutral chloro alkyl bisphosphate class, neutral chlorinated phosphonate class and composition thereof.Most preferred matrix material example is included in organic group R xIn the ester class of neutral organophosphorus of a carbon containing, hydrogen and oxygen.
Though the most of binder compound that the present invention includes is the goods that satisfy above-listed three standards that can buy from the market, some compound is not like this.But these binding agents can be handled by the inventive method, make it to satisfy these standards.This method is illustrated by the following examples, but is not limited on this embodiment.
Embodiment 1
The structure that illustrates below illustrates the poly-amido phosphonate that can buy on a kind of market:
Figure 891040471_IMG18
This commercially available compound is 50% aqueous solution; This solution is strongly-acid during purchase, therefore is not suitable for purpose of the present invention.
According to the inventive method, add a kind of solution alkaline matter (as the NaOH) neutralization, be not less than 10 to pH, preferably be not less than 12.Distill this solution then to removing whole water basically.Replace water with commercially available organic solvent (as ethylene glycol etc.).Gained gets consisting of of adhesive solvent: 50-60% ethylene glycol, 10-20%H 2O, all the other are phosphonic acid esters.
Need there be 10-20% water in this specific binder solution, so that the phosphonic acid ester binding agent is dissolved in the ethylene glycol fully.With the refractory material aggregate binder mixtures made from this particular adhesive solution, the shelf-life reaches 6 months approximately, has quite high cold crushing strength with the refractory product of this mixture production.
Though this embodiment adopts ethylene glycol medium, the many binder compounds that the present invention includes can have been bought the liquid product, so do not need it is dissolved among the organic solvent.
Binding agent of the present invention can together use the premixed lay-by material of preparation with the ceramic fire resistant aggregate, and this material can be used to build, rebuild or repair the furnace lining of industrial furnace etc.Advantage of the present invention is that this refractory aggregate/binder mixtures needn't " on the spot " prepare, and all other known aqueous alkaline refractory aggregate/binder mixtures all requires to prepare on the spot.The inventor etc. have at first found a class phosphorated binding agent, this binding agent can mix with alkalescence (and non-alkalescence) refractory aggregate, make can long storage mixture, this mixture is under the premixed backup form and does not contain the Degradation that effect or chemical reaction cause because of water.
With liquid form binding agent of the present invention is added in the refractory aggregate, makes a kind of premixed standby mixture discussed above.The preferred 0.1-20%(weight of the amount of binding agent), more preferably 0.1-10%.If the consumption of binding agent is less than 0.1%(weight), then aggregate can not be together well-bonded.If the binding agent consumption is higher than 20%(weight), then excessive phosphorus forms a kind of glassy phase, thus refractory product intensity and the thermotolerance of using this mixture to make all reduce.
Mixture of the present invention can be used for realizing more known purposes in the fire resisting material field.Apply this mixture when needing, be heated to temperature then and be higher than on the decomposition temperature of said organic materials (being generally 500 °F) so that between refractory material aggregate, produce cohesive action.Aryl and alkyl composition generally speaking, and the alkyl that replaces and the aryl composition of replacement burn, and stays active phosphorus substance (being phosphoric acid, acid phosphate and acid phosphonate etc.), generates binding agent with the refractory aggregate reaction.
The using method of refractory aggregate-binder mixtures of the present invention comprises: prepare premixed refractory aggregate binder mixtures, long time stored this mixture, apply this mixture on the refractory liner of stove then this mixture of thermal treatment form and have high-intensity bonding refractory materials base substrate.
The present invention also provides a kind of refractory materials base substrate of being made by premixed standby refractory aggregate-binder mixtures.Read more following embodiment and can know that the refractory materials base substrate of being made by refractory aggregate/binder mixtures of the present invention has high cold crushing strength.
Following all embodiment are for more detailed introduction and explanation the present invention.What should emphasize is that these embodiment are illustrative purely, invention should not be construed as other characteristics that do not occur among these embodiment that are not included in.
Embodiment 2
Press the periclasite and 7%(weight of the high-density 98%MgO of known graded particie distributes in the fire resisting material field (A graded particle size distribution)) three (2-chloropropyl) phosphoric acid ester mix.According to the ASTM(American Standard of Testing Materials) essentially identical mode ramming described in the Test c 181-82 " machinability rating of fireclay and high-alumina fireclay plastic refractory ", prepare some little garden posts.With these little garden posts and following whole other samples, according to heat-treating with essentially identical mode described in the ASTM Test c856-77 " firing of refractory concrete sample ", in electrothermal oven, handled respectively 5 hours under 1000,1800,2500 and 2910 temperature, measure the cold crushing strength under every kind of treatment temp then respectively, its value is respectively 2671,2487,4488 and 5114 pounds/square inch.
Embodiment 3
Except the aggregate that uses 88%MgO, by top embodiment 2 preparation samples.These samples of thermal treatment under 1000,1800,2500 and 2910 temperature respectively, shown cold crushing strength is respectively 1361,1833,5514 and 11944 pounds/square inch.
Embodiment 4
Except graded particie distributes by 50%(weight) magnefer and surplus be for the 98%MgO periclasite forms, and press the foregoing description 2 and prepare samples.These samples are thermal treatment under 1000,1800,2500 and 2910 temperature respectively, and the cold crushing strength that demonstrates is respectively 1275,2204,5739 and 7216 pounds/square inch.
Embodiment 5
Preparation contains the sample of the foregoing description 4 described rhombspar/periclasite aggregates.With these samples and 2-7%(weight) three (2-chloropropyl) phosphoric acid ester mix, and, under 1000,1800,2500 and 2910 °F, heat-treat according to the mode ramming that is similar to ASTM Test c181-82.The cold crushing strength of each sample is as follows:
Scope No. 2 No. 3 No. 4 No. 5 No. 6 No. 7
（1000°F） 94 306 668 848 1085 1275
Normal temperature is withstand voltage (1800) 150 433 965 1,214 1,658 2204
Intensity (2500) 1,808 2,543 2,826 2,722 4,208 5739
Pound/square inch (2910) 4,227 6,476 7,070 5,803 6,877 7216
Embodiment 6
Except fine aggregate, prepare some samples by top embodiment 2 described methods; Said aggregate comprise account for mixture 2%(weight) chromic oxide and the material formed by the periclasite of 2% silicon metal and 98%MgO of surplus.Under 1000,1800,2500 and 2910 temperature sample is heat-treated respectively, their shown cold crushing strengths that goes out are respectively 3747,2841,6011 and 7320 pounds/square inch.
Embodiment 7
By top embodiment 2 some samples of preparation, be divided into two Lot samples then.1000 thermal treatments, record cold crushing strength is 1318 pounds/square inch to the A Lot sample after mixing.The B Lot sample wore out four months under no outward appearance curing condition, and then 1000 following thermal treatments, recording cold crushing strength is 1526 pounds/square inch.
Embodiment 8
The periclasite and 7%(weight of the high-density 98%MgO that graded particie is distributed) the chloroethyl phosphoric acid ester of dichloro neo-pentyl ethylene glycol mix.According to the described essentially identical method ramming of ASTM Test c181-82, prepare some little Cylinders.With the thermal treatment under 1000,1800,2500 and 2910 temperature respectively of these samples, record cold crushing strength and be respectively 1223,1588,1724 and 1473 pounds/square inch.
Embodiment 9
Except the aggregate that uses 88%MgO, by top embodiment 8 preparation samples, thermal treatment sample under 1000,1800,2500 and 2910 temperature records cold crushing strength and is respectively 1152,2057,3490 and 7376 pounds/square inch respectively.
Embodiment 10
Except coarse aggregate is to account for mixture 50%(weight) magnefer and the periclasite of surplus 98%MgO, by top embodiment 8 preparation samples.Thermal treatment sample under 1000,1800,2500 and 2910 temperature records cold crushing strength and is respectively 1408,1012,1581 and 2840 pounds/square inch.
Embodiment 11
Except only using 3-0.5%(weight) the chloroethyl phosphoric acid ester of dichloro neo-pentyl ethylene glycol, press the foregoing description 8 preparation samples, spent glycol is diluted to content liquid and reaches 7%(weight), these samples of thermal treatment under 1000,1800,2500 and 2910 temperature record cold crushing strength and are respectively 1022,967,1341 and 1513 pounds/square inch respectively.
Embodiment 12
Press the foregoing description 8 preparation samples, and be divided into two batches.The A Lot sample mixes back thermal treatment under 1000 temperature, and its cold crushing strength is 2526 pounds/square inch.Under no apparent hardened condition, made the B Lot sample aging 4 months, thermal treatment under 1000 temperature then, recording cold crushing strength is 2201 pounds/square inch.
Embodiment 13
Except using the poly-aminophosphonic acid of soda neutral, by top embodiment 2 preparation samples.Thermal treatment sample under 1000,1800,2500 and 2910 temperature records cold crushing strength and is respectively 685,531,3114 and 2488 pounds/square inch respectively.
Embodiment 14
The material that three kinds of graded particies are distributed (periclasite of a kind of 98%MgO of containing, the aggregate of a kind of 88%MgO of containing and a kind of contain weight) rhombspar and 550%(weight by 50%() the mixture formed of the periclasite that contains 98%MgO) with 7%(weight) the mixture of forming by chloropropyl and chloroethyl phosphoric acid (phosphonic acids) ester mix.Utilize the ramming legal system to be equipped with small sample, thermal treatment 5 hours under 1000,1800,2500 and 2910 temperature respectively, its cold crushing strength value is as follows:
Composition 98% MgO 50% rhombspar
Periclasite 88% MgO 50% periclasite
（1000°F） 3025 2471 3235
Normal temperature is withstand voltage (1800) 3,736 3,455 4807
Intensity (2500) 4,108 6,505 7966
(pound/square inch) (2910) 3,934 14,850 12,719
Embodiment 15
Except in Sample A, using 7%(weight) below phosphoric acid ester/phosphonic acid ester mixed ester of listing:
X=0 or 1 in the formula, and in sample B, use 7%(weight) outside the mixture of forming by chloroethyl phosphoric acid ester and chloropropyl phosphoric acid ester, prepares samples by top embodiment 2.Thermal treatment sample under 1000,1800,2500 and 2910 temperature respectively, the result is as follows for its cold crushing strength:
Composition A B
（1000°F） 1965 1674
Cold crushing strength (1800) 1,803 2252
(pound/square inch) (2500) 1,131 2678
（2910°F） 1262 2222
Embodiment 16
Except with 50%(weight) periclasite that contains 98%MgO and 45-49%(weight) magnefer respectively with 1-5%(weight):
A) three (2-chloropropyl) phosphoric acid ester,
B) propenoxylated dibutyl pyrophosphoric acid and
C) three (fourth oxygen ethyl) phosphoric acid ester
Outside the mixing, according to the foregoing description 2 preparation samples.Handle sample respectively under 1000,1800,2500 and 2910 temperature, the cold crushing strength value that records is as follows:
Mixture A (5%) (4%) (3%) (2%) (1%)
1000 848 668 306 94 46 of cold crushing strength
(pound/square inch) 1800 °F 1,214 965 433 150 96
2500°F 2722 2826 2543 1808 3584
2910°F 5803 7070 6476 4227 3738
Mixture B (4%) (3%) (2%) (1%)
1000°F 995 291 286 195
1800 1,368 439 399 283 of cold crushing strength
(pound/square inch) 2500 °F 3,980 4,358 3,748 4345
2910°F 5110 5008 4405 4910
Mixture C (4%) (3%) (2% (1%)
1000°F 635 348 120 14
1800 776 470 160 29 of cold crushing strength
(pound/square inch) 2500 °F 6,191 3,967 3,333 1806
2910°F 9206 5708 5864 4600
Though the every kind of binding agent that utilizes among the above-listed embodiment all is monomeric compounds, be to use the polymkeric substance that contains these materials and multipolymer also fully within the scope of the present invention.In addition, as institute among the embodiment was in the above seen, the mixture of phosphoric acid ester, phosphonic acid ester and phosphonate (for example mixture of chloroethyl and chloropropyl phosphoric acid ester and phosphonic acid ester) also belonged to the scope of the invention fully.
Though the present invention introduces under specified conditions to a certain degree, should know on specific open that the present invention is not limited to that this paper comprises; And the present invention can comprise various variations, distortion and improvement that those skilled in the art may make under not exceeding the scope of the invention condition of stipulating in the appended claim.

Claims (9)

1, a kind of anhydrous basically refractory aggregate and binder mixtures with long storage life limit wherein comprises:
0.1-20% (weight) neutral phosphorated organic adhesive immunomodulator compounds or its homopolymer or multipolymer, and
The refractory aggregate of 80-99.9% (weight),
When heating, wherein said binding agent between said refractory aggregate, forms the phosphorated binding material.
2, according to the mixture of claim 1, wherein said refractory aggregate is alkaline refractory aggregate.
3, according to the mixture of claim 2, wherein said alkaline refractory aggregate comprises and is selected from the aggregate group that is formed by periclasite, magnefer, magnesite and its binding substances at least a aggregate as main component.
4, according to the mixture of claim 1, wherein said binder compound exists with liquid phase or the solid phase form that is dissolved in the liquid organic medium.
5, according to the mixture of claim 1, wherein said binder compound amount is a 0.1-10%(weight).
6, a kind of anhydrous basically refractory aggregate and binder mixtures with long storage life limit wherein comprises:
1) binder compound 0.1-20%(weight), said binder compound comprises the phosphoric acid ester with following formula structure:
R wherein 1=, ≠ R 2=, ≠ R 3, and R 1, R 2And R 3Comprise the alkyl of alkyl, aryl, replacement and the aryl of replacement, wherein on said alkyl or aryl or interior substituting group be selected from the group group of forming by following groups:
And
2) refractory aggregate 80-99.9%(weight):
When heating, wherein said binder compound between said refractory aggregate, forms the binding material of phosphorous acid esters.
7, a kind of anhydrous basically refractory aggregate and binder mixtures with long storage life limit wherein comprises:
1) adhesive compound 0.1-20%(weight), said adhesive compound comprises the phosphonic acid ester with following structural:
R wherein 1=, ≠ R 2=, ≠ R 3, and R 1, R 2And R 3Comprise the alkyl of alkyl, aryl, replacement and the aryl of replacement, wherein on said alkyl or aryl or interior substituting group be selected from the group group of forming by following groups:
Figure 891040471_IMG4
And
2) refractory aggregate 80-99.9%(weight);
When heating, wherein said binder compound between said refractory aggregate, forms the phosphorated binding agent.
8, a kind of anhydrous basically refractory aggregate and binder mixtures with long storage life limit, comprising:
1) 0.1-20%(weight) comprise binder compound with following formula structure phosphonate:
Figure 891040471_IMG5
M wherein 1=, ≠ M 2, and M 1And M 2Be selected from by Na +, K +And Li +The ionic group of forming, and R comprises the alkyl of alkyl, aryl, replacement or the aryl of replacement, wherein on said alkyl or aryl or interior substituting group be selected from the group group of forming by following groups:
Figure 891040471_IMG6
And
2) refractory aggregate 80-99.9%(weight);
Wherein said binder compound heating forms the phosphorated binding material down between said refractory aggregate.
9, a kind of anhydrous basically refractory aggregate and binder mixtures with long storage life limit is comprising neutral phosphorated organic compound or its homopolymer or multipolymer; Wherein said binding agent does not at room temperature react basically with refractory aggregate, exists with the liquid phase or the solid phase that can be dissolved in organic solvent, is decomposed to form active phosphorated material before being heated to boiling.
CN89104047A 1988-06-16 1989-06-16 The fire-resistant product that refractory aggregate improves to some extent with low temperature bonding immunomodulator compounds and normal temperature strength Pending CN1040188A (en)

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US20719988A 1988-06-16 1988-06-16
US207,199 1988-06-16
US271,657 1988-11-16
US07/271,657 US4981821A (en) 1988-06-16 1988-11-16 Low temperature binder compound for refractory aggregates and refractory products of improved cold strength

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US (1) US4981821A (en)
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JP (1) JPH03505081A (en)
KR (1) KR900701690A (en)
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AU (1) AU641124B2 (en)
CA (1) CA1332246C (en)
WO (1) WO1989012610A1 (en)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN108350574A (en) * 2015-10-06 2018-07-31 恩特格里斯公司 The cold sintering of solid precursors

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US5268338A (en) * 1992-03-31 1993-12-07 The J. E. Baker Company Ceramic adhesive composition and use thereof
US5362690A (en) * 1992-12-16 1994-11-08 Ceram Sna Inc. Refractory castable composition and process for its manufacture
ATE281419T1 (en) * 1997-05-17 2004-11-15 Vesuvius Uk Ltd CASTABLE FIREPROOF COMPOSITION
CN111943692B (en) * 2020-06-30 2022-05-10 辽宁东和新材料股份有限公司 High-performance magnesia-calcium brick and preparation method thereof

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US3549473A (en) * 1968-01-02 1970-12-22 Monsanto Co Binder composition and uses
US3950177A (en) * 1970-03-16 1976-04-13 Imperial Chemical Industries Limited Refractory compositions
JPS5540770B2 (en) * 1973-07-28 1980-10-20
JPS5532675B2 (en) * 1974-09-30 1980-08-26
DE2729077A1 (en) * 1977-06-28 1979-01-11 Bayer Ag Low density inorganic tiles - made by bonding hollow siliceous spheres with phosphate(s)
JPS589067B2 (en) * 1978-06-19 1983-02-18 日本化学工業株式会社 Refractory raw material composition
JPS5978747A (en) * 1982-10-28 1984-05-07 Aisin Chem Co Ltd Resin-coated sand grain for shell mold

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108350574A (en) * 2015-10-06 2018-07-31 恩特格里斯公司 The cold sintering of solid precursors
CN108350574B (en) * 2015-10-06 2020-06-05 恩特格里斯公司 Cold sintering of solid precursors

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US4981821A (en) 1991-01-01
WO1989012610A1 (en) 1989-12-28
CA1332246C (en) 1994-10-04
AU641124B2 (en) 1993-09-16
EP0419552A1 (en) 1991-04-03
KR900701690A (en) 1990-12-04
JPH03505081A (en) 1991-11-07
AU3841789A (en) 1990-01-12

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